OH自由基引发光氧化氟氯碳化合物的研究

研究了ＣＦＣ－１１＋Ｈ２Ｏ２，ＣＦＣ－１１＋Ｈ２Ｏ２＋Ｏ２，ＣＦＣ－１２＋Ｈ２Ｏ２和ＣＦＣ－１２＋Ｈ２Ｏ２＋Ｏ２４个体系的光化学反应，这些体系在低压尔照射下，Ｈ２Ｏ２产生了ＯＨ自由基，ＯＨ自由基能引发ＣＦＣ的光氧化反应，其产物在２０ｍ长的漪避用富叶红外光谱仪测量，发现在ＣＦＣ－１１＋Ｈ２Ｏ２和ＣＦＣ－１１＋Ｈ２Ｏ２＋Ｏ２体系中有ＣＯＦＣｌ，ＣＯ２和ＨＣｌ，而在ＣＦＣ－１２＋Ｈ２Ｏ２和ＣＦＣ－１２＋     

聚氨酯固化剂清洁生产技术分析

研究以一个利用分子蒸馏技术生产聚氨酯固化剂的大型新建项目为例,对其原料、产品、工艺和设备进行类比分析,提出了在聚氨酯固化剂生产中推行清洁生产的建议和措施,以期为制造单位在今后的工艺、工程设计、清洁生产和环境管理等方面提供一些科学依据。     

电Fenton法处理难降解有机物的研究进展

评述了电Fenton法在水处理的中的应用状况及国内外研究现状，介绍了各种电Fenton法进行机理及存在的优缺点，并对其今后的发展趋势进行了阐述。     

Mechanism and kinetics study on the ozonolysis reaction of 2,3,7,8-TCDD in the atmosphere

The ozonolysis of 2,3,7,8-tetra-chlorodibenzo-p-dioxin(2,3,7,8-TCDD) is an efcient degradation way in the atmosphere. The ozonolysis process and possible reactions path of Criegee Intermediates with NO and H2 O are introduced in detail at the method of MPWB1K/6-31+G(d,p)//MPWB1K/6-311+G(3df,2p) level. In ozonolysis, H2O is an important source of OH radical formation and initiated the subsequent degradation reaction. The Rice-Ramsperger-Kassel-Marcus(RRKM) theory was applied to calculate rate constants with the temperature ranging from 200 to 600 K. The rate constant of reaction between 2,3,7,8-TCDD and O3 is 4.80 × 10 20cm3/(mole·sec) at 298 K and 760 Torr. The atmospheric lifetime of the reaction species was estimated according to rate constants, which is helpful for the atmospheric model study on the degradation and risk assessment of dioxin.     

Mechanisms of photochemical release of dissolved organic matter and iron from resuspended sediments

Photochemical reactions can alter the transformation of sedimentary organic matter into dissolved organic matter (DOM) and affect its ultimate fate in water ecosystems. In the present study, the photorelease of DOM and Fe from resuspended lake sediments was investigated under different O₂ and NO₃^? concentration conditions to study the mechanisms of DOM and Fe photorelease. The amount of photoreleased Fe, which ranged from 0.22 to 0.70 μmol/L, was significantly linearly correlated with the amount of photoreleased DOM. O₂ and NO₃^? could promote the photochemical release of DOM and Fe, especially during the initial 4 h irradiation. In general, the order of the photorelease rates of DOM and Fe under different conditions was as follows: NO₃^?/aerobic > aerobic ≈ NO₃^?/anaerobic > anaerobic. The photorelease rates of DOM and Fe were higher for the initial 4 hr irradiation than these for the subsequent 8 hr irradiation. The photorelease of DOM and Fe is thought to proceed via direct photodissolution and indirect processes. The relative contributions of indirect processes (>60%) was much greater than that of direct photodissolution (<40%). The photoproduced H₂O₂ under aerobic and anaerobic conditions indicated that hydroxyl radicals (?OH) are involved in the photorelease of DOM. Using ?OH scavengers, it was found that 38.7%, 53.7%, and 77.6% of photoreleased DOM was attributed to ?OH under anaerobic, aerobic, and NO₃^?/aerobic conditions, respectively. Our findings provide insights for understanding the mechanisms and the important role of ?OH in the DOM and Fe photorelease from resuspended sediments.     

Detection of intermediates in the TiO2-assisted photodegradation of Rhodamine B under visible light irradiation

The photocatalytic degradation of dye Rhodamine B （RhB） in the presence of TiO2 nanostdpe or P25 under visible light irradiation was investigated. The degradation intermediates were identified using Infrared spectra （IR spectra）, ^1H nuclear magnetic resonance （^1HNMR） spectra, and gas chromatography-mass spectroscopy （GC-MS）. The IR and the ^1HNMR results showed that the large conjugated chromophore structure of RhB was efficiently destroyed under visible light irradiation in both the photocatalytic systems （TiO2 nanostfipe or P25 and Rhodamine B systems）. GC-MS results showed that the main identified intermediates were ethanediotic acid, 1,2-benzenedicarboxylic acid, 4-hydroxy benzoic acid and benzoic acid, which were almost the same in the TiO2 nanostdpes and P25 systems. This work provides a good insight into the reaction pathway（s） for the TiO2-assisted photocatalytic degradation of dye pollutants under visible light irradiation.     

环境温度对粉尘爆炸参数的影响

研究了环境温度对萘酐(C10H6O2)粉尘爆炸参数的影响,得到了随着温度的升高,最大爆炸压力峰值变化不大;而最大压力上升速率增大,爆炸下限浓度降低,安全氧含量也会降低.根据化学动力学理论对这一影响进行了分析.     

低溶解氧下SBR内短程硝化影响因素试验研究

为了明确低溶解氧下短程硝化的其它控制因素,文章采用序批式反应器(SBR)系统研究了低溶解氧下实现短程硝化影响因素的控制范围。试验结果表明:SBR内较高的游离氨浓度(0.50～20.73 mg/L)对亚硝酸的积累起到一定促进作用;实现低溶解氧下短程硝化的温度和泥龄范围较大,在温度为21～30℃、泥龄为15～40 d的范围内都可以实现稳定的短程硝化,实验过程中亚硝酸积累率一直维持在80%以上;有机物的存在对氨氧化速率影响不大,但高有机物浓度(COD为900 mg/L)下,SBR内发生了高粘性膨胀。     

基于质子转移反应质谱(PTR-MS)对北方冬季大气氨的观测研究

氨是大气中广泛存在的碱性气体,已有的研究表明,氨能够参与包括硫酸/水体系的三元成核过程,进而促进新粒子的形成;同时,氨也是大气二次有机气溶胶（SOA）的重要前体物,对二次有机气溶胶的形成具有不可忽视的影响.了解大气中氨的污染情况,实现对大气中氨的高时间分辨率的在线观测,对于研究大气中氨的时空分布及来源解析,进而加深对气溶胶生成机理及气溶胶在大气辐射平衡与气候变化中作用的认识有重要意义.本研究使用一台自主搭建的质子转移反应质谱仪（PTR-MS）,以丙酮作为反应试剂,由电晕放电离子源产生质子化的丙酮反应试剂离子（（C₃H₆O）_nH⁺）（n=1,2）,与大气中的气态氨及其他碱性气体发生质子转移反应后进行质谱检测.丙酮（C₃H₆O）相较于水（H₂O）和乙醇（C₂H₅OH）,具有更高的质子亲和力（PA=194.1 kcal·mol^-1）,对PA较高的碱基化合物的选择性更好,可减少其他物质对四极杆质谱检测结果的影响.本研究在2017年11月9日—2018年1月10日和2018年11月12日—2019年1月2日华北地区气溶胶生成机理综合研究联合外场观测期间,将PTR-MS部署于山东省德州市平原县气象局观测场内,对大气中的氨气进行实时在线观测.结果表明,两次观测的气态氨平均值分别为（5.89±5.27）ppbv和（2.65±2.41）ppbv,均呈现出一个明显的日变化规律,即上午6：00—7：00出现峰值,随后逐渐下降,在下午大约15：00浓度达到最低值,随后上升.结合正交矩阵因子分解法（Positive Matrix Factorization,PMF）模型对当地近地面大气中氨气进行初步的来源分析,发现当地大气中氨气的来源主要是周边农村在冬季大量使用生物质燃料燃烧取暖造成的生活排放和当地交通源排放.两次冬季观测中当地农村取暖等生活排放分别占到66.0%和55.0%;交通排放在两次观测中分别占到27.0%和36.8%;农田土壤释放、畜牧养殖排放和工业排放等其他来源占比较低,分别是6.2%和7.5%;外部传输来源只占到很少一部分,分别是0.8%和0.7%.2018年的冬季观测相较于2017年,氨气浓度总体出现下降,主要来源还是以当地农村冬季生活和取暖燃烧排放为主,但通过相关政策管控,这一污染来源得到改善.     

十字花科植物中的芥子碱对果蝇的抗衰老作用

芥子碱对Ｏ－２和ＯＨ的清除效率达５０％时的质量浓度（ρ）分别为５ｍｇＬ－１和３３０ｍｇＬ－１,４０ｍｇＬ－１的芥子碱对Ｏ－２的清除效率即可达８９．７％,证明芥子碱是一Ｏ－２与ＯＨ的清除剂．分别以ρ为１０ｍｇＬ－１和５０ｍｇＬ－１芥子碱的培养基饲喂果蝇,对果蝇的最高寿命、平均寿命及半数寿命均有一定的延长作用,其中１０ｍｇＬ－１的芥子碱组可明显延长雄性果蝇的最高寿命（１１．９０％）、平均寿命（１１．２４％）及半数寿命（１７．２１％）,两种浓度的芥子碱溶液对果蝇的平均寿命的延长作用的差异显著．芥子碱对果蝇的延寿作用有一定的性别差异,对雄蝇的效果好于雌蝇